Method of manufacturing non-firing type electrode

ABSTRACT

A method of manufacturing a non-firing type electrode comprising steps of: (A) applying on a substrate a conductive paste comprising, (a) a conductive powder comprising, (i) a first conductive powder having Young&#39;s modulus of 60×10 9  Pa or higher; and (ii) a second conductive powder having Young&#39;s modulus of 5×10 9  to 50×10 9  Pa; and (b) an organic vehicle, (B) heating the applied conductive paste at 50 to 350° C. to form an electrode; and (C) pressing the electrode at 10 to 1000 kN/m 2  of plane surface pressure or at 5 to 300 kN/m of linear pressure.

FIELD OF INVENTION

The present invention relates to a method of manufacturing a non-firingtype electrode.

TECHNICAL BACKGROUND OF THE INVENTION

Non-firing type electrodes are widely used in various electricaldevices. The term “non-firing type electrode” is defined as an electrodeformed without a heat treatment at temperature of 350° C. or higher.

US20090169724 discloses a method for producing a non-firing typeelectrode of membrane touch switch by (a) screen printing a conductivepaste containing silver powder, phenoxy resin, urethane resin and anorganic solvent on a polymer film, and (b) heating the printedconductive paste at 140° C.

BRIEF SUMMARY OF THE INVENTION

An objective is to provide a method of manufacturing a non-firing typeelectrode which can have sufficient electrical property despite of usingless conductive metal powder.

An aspect of the invention relates to a method of manufacturing anon-firing type electrode comprising steps of: (A) applying on asubstrate a conductive paste comprising, (a) a conductive powdercomprising, (i) a first conductive powder having Young's modulus of60×10⁹ Pa or higher; and (ii) a second conductive powder having Young'smodulus of 5×10⁹ to 50×10⁹ Pa; and (b) an organic vehicle, (B) heatingthe applied conductive paste at 50 to 350° C. to form an electrode; and(C) pressing the electrode at 10 to 1000 kN/m² of plane surface pressureor at 5 to 300 kN/m of linear pressure.

Another aspect of the invention relates to an electrical devicecomprising the non-firing type electrode manufactured by the methodabove.

The non-firing type electrode having sufficient conductivity can beformed by the present invention. Moreover the consumption of the firstconductive powder can reduce by the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1, A to C, explains an embodiment of the method of manufacturingthe electrode in the present invention.

FIG. 2 illustrates an embodiment of roll to roll system in the step ofpressing the electrode by a calendar roll.

FIG. 3 is pictures of the electrode surface before and after pressing inExample 3 (upper) and Example 6 (lower).

DETAILED DESCRIPTION OF THE INVENTION

The method of manufacturing the non-firing type electrode comprisessteps of (A) applying on a substrate a conductive paste, (B) heating theapplied conductive paste to form an electrode, and (C) pressing theelectrode. The method and materials to form non-firing type electrodeexplained below.

Method of Manufacturing an Electrode

An example of the method of manufacturing the non-firing type electrodeis explained with reference to FIG. 1A to 1C.

The conductive paste 10 is applied onto a substrate 11 as illustrated inFIG. 1A. To apply the conductive paste on the substrate, screenprinting, stencil printing, gravure printing, offset printing, spincoating, blade coating, casting, or nozzle discharge can be available.The screen printing can be selected because the paste can be quicklyscreen printed in the desired pattern on a substrate in an embodiment.

The substrate 11 can be glass substrate, polymer film, semiconductorsubstrate, ceramic substrate or metal substrate in an embodiment. Thesubstrate 11 can be selected depending on electrical devices, forexample a glass or polymer substrate for touch panel, a semiconductorsubstrate for solar cell, and a ceramic substrate for capacitor or chipresistor. A metal substrate that has good thermal conductivity can besuitable for electrical devices that need heat radiation such as a lightemitter diode (LED). When the substrate 11 is a metal substrate or asemiconductor substrate, an insulating layer can be formed on thesubstrate 11 to not get electrical continuity between the substrate andthe formed electrode.

In an embodiment, the substrate 11 can be a polymer film. Polymer filmis in general flexible enough to not be broken by pressing. The polymerfilm can be a polyethylene terephthalate (PET) film, polyethylenenaphthalate (PEN) film, polyimide (PI) film, polyimideamide film,polyamide film, polypropylene film, or polyethylene film. In the eventof heating the conductive paste at over 100° C. in the later heatingstep, the polymer substrate can be the polymer film having heatresistance such as the PET film, PEN film or the PI film.

The applied conductive paste 10 on the substrate 11 is heated. Byheating, the applied conductive paste which is viscous can becomenon-viscous enough to not be adhesive to a pressing tool in thesubsequent pressing step. The heating temperature is 50 to 350° C., 60to 250° C. in another embodiment, 70 to 200° C. in another embodiment.The heating time can be 1 to 120 minutes in an embodiment, 3 to 90minutes in another embodiment, 5 to 50 minutes in another embodiment. Inthe event that the conductive paste is heat-curable, the applied pastecan get cured by evaporations of solvent and/or by the molecularstructure in the thermosetting polymer turned into net-like structureunder the heat.

In another embodiment, the conductive paste can be heated at 50 to 120°C. just to become non-viscous before the pressing step (C). Theelectrode can be heated again after the pressing step (C) at relativelyhigh temperature, for example 100 to 350° C., to be firmly cured. In theevent of heating the electrode twice, the method of manufacturing anon-firing type electrode comprising steps of: (A) applying a conductivepaste on a substrate; (B) heating the applied conductive paste at 50 to120° C. to form an electrode; (C) pressing the electrode at 10 to 1000kN/m² of plane surface pressure or at 5 to 300 kN/m of linear pressure;and (D) heating the pressed electrode at 100 to 350° C., in anembodiment. The heating temperature in the heating step (D) can be 110to 220° C. in another embodiment, 120 to 180° C. in another embodiment.

A heating machine such as an oven, a dryer, and a furnace that cancontrol the temperature can be used for heating.

The electrode can be obtained by heating the applied conductive paste.The applied conductive paste which is non-viscous by being heated tohave electrical conduction is called “electrode” in this specification.

In an embodiment, the electrode is pressed at 5 to 300 kN/m of linearpressure in the direction of P1, which is the perpendicular direction tothe plane of the boundary between the electrode 101 and the substrate11, by a roll 12 moving on the upper surface of the electrode 101 in thedirection of D1, which is parallel to the plane of the boundary betweenthe electrode 101 and the substrate 11, as illustrated in FIG. 1B andFIG. 1C.

The linear pressure is a pressure on line on the upper and/or rearsurface of the electrode. The linear pressure moves to one direction topress entire upper surface and/or rear surface of the electrode.

The pressure strength can be selected according to, for example,thickness of the electrode, kind of the conductive powder, or type ofthe substrate. The linear pressure can be 22 to 200 kN/m in anotherembodiment, 35 to 125 kN/m in another embodiment, and 45 to 98 kN/m instill another embodiment. By being pressed in such range, resistivity ofthe electrode can be lowered as shown in Example below.

In the event of employing the liner pressure, the substrate 21 on whichthe electrode is formed can be a continuous roll 22 and pressed with thecalendar roll 20 in a roll to roll system in another embodiment asillustrated in FIG. 2. The substrate can be a polymer film which isflexible enough to make the roll 22 when employing the roll to rollsystem. The substrate 21 is threaded through the calendar roll 20 whichlinearly presses the electrode on the substrate. “Calendar” is ingeneral a machine having two or more rolls to thread a substance betweenthe rolls to press the substance.

The electrode 101 can be also pressed at 10 to 1000 kN/m² of planesurface pressure. The plane surface pressure is a pressure on the entireupper and/or rear surface of the electrode 101 at the same time. Anymethod to make the plane surface pressure can be available, for examplecrank press, crankless press, or knuckle joint press. Presumptively airbubbles between the conductive particles in the electrode could bepushed out of the electrode by the press to result in getting highconductivity.

The surface pressure can be 32 to 720 kN/m² in another embodiment, 65 to580 kN/m² in another embodiment, and 100 to 470 kN/m² in still anotherembodiment.

The pressing is carried out just once or twice in an embodiment. Theelectrode could obtain lower resistivity by pressing just once as shownin Example below. Being pressed three times or more could damage theelectrode and the substrate.

In an embodiment, the method further comprises a step (D) of secondlyheating the electrode to firmly cure after the pressing step (C). Theheating temperature of the second heating after the pressing step can be100 to 350° C. in an embodiment, 110 to 220° C. in another embodiment,120 to 180° C. in another embodiment.

The method of manufacturing the electrode can optionally employphotolithography. In the event of photolithographic method, theconductive paste is photosensitive and the method can further contain astep of exposing the electrode to light to cure between the step ofheating (B) and the step of pressing (C) or after the step of pressing(C). In another embodiment, the method of manufacturing the non-firingtype electrode comprises steps of (A) applying on a substrate aconductive paste, (B) heating the applied conductive paste to form anelectrode, (E) exposing the electrode to light, and (C) pressing theelectrode. In another embodiment, the method of manufacturing thenon-firing type electrode comprises steps of (A) applying on a substratea conductive paste, (B) heating the applied conductive paste to form anelectrode, (C) pressing the electrode, (E) exposing the electrode tolight.

The exposing condition can be controlled according to photosensitivityof the photosensitive paste and thickness of the applied conductivepaste. The cumulative exposure is 50 to 2000 mJ/cm² in an embodiment.

When the conductive paste or the substrate is unfavorable to be wet, theelectrode is formed by applying the conductive paste with a desiredpattern and exposed to light without an aqueous development.

However when both of the substrate and the electrode are fine to be wet,the exposing step can be followed by a developing step with an aqueoussolution. The photolithographic method using the developing step isadvantageous especially when forming a fine pattern. The fine patterncan comprises lines with width of 1 to 200 μm and space between thelines of 1 to 200 μm in an embodiment; width of 5 to 160 μm and spacebetween the lines of 3 to 160 μm in another embodiment; width of 10 to110 μm and space between the lines of 3 to 110 μm in another embodiment.The thickness of the fine pattern electrode can be 1 to 20 μm in anembodiment.

The aqueous solution can be an alkaline solution such as a 0.4% sodiumcarbonate solution. The aqueous solution can be sprayed to the exposedconductive paste to remove the unexposed area of the conductive paste sothat the cured pattern by the photo-energy shows up.

For the photolithographic method and photosensitive conductive paste,US5143819, US5075192, US5032490, US7655864 can be herein incorporated byreference.

The method of manufacturing the non-firing type electrode can beapplicable to any electrical devices. In an embodiment, the electricaldevices such as solar cell, resistor, capacitor, heater, touch panel,sensor, membrane touch switch, and defogger on an automotive window cancontain the non-firing type electrode manufactured by the methodexplained above.

Conductive Paste

The conductive paste used in the method can be any type such asheat-curable and photosensitive. The conductive paste comprises at least(a) a conductive powder and (b) an organic vehicle. The conductive pastematerials are explained in detail below.

(a) Conductive Powder

The conductive powder is a powder made of any material having electricalconductivity. The conductive powder is 100 parts by weight in anembodiment. The conductive powder is 55 to 98 weight percent (wt %) inan embodiment, 68 to 96 wt % in another embodiment, and 75 to 93 wt % instill another embodiment based on the weight of the conductive paste.

The conductive powder comprises (i) a first conductive powder havingYoung's modulus of 60×10⁹ Pa or higher, and (ii) a second conductivepowder having Young's modulus of 5×10⁹ to 50×10⁹ Pa.

Young's modulus, also known as the tensile modulus, is a measure of thestiffness of a material calculated as follows.

Young's modulus=T/S

where T is tension calculated as [(Stress (N))/(Cross section area(m²))], and S is strain ratio calculated as [(Length of the materialunder the tension T (m)−Original length of the material (m))/Originallength of the material (m)].

The first conductive powder having relatively high Young's modulus ishard so that the particles hardly deform by being pressed in thepressing step. The second conductive powder having relatively lowYoung's modulus is soft so that the powder could deform by being pressedconsequently to fill space between the first conductive powder particlesand connect the particles.

(i) First Conductive Powder

The first conductive powder is a metal powder having Young's modulus of60×10⁹ Pa or higher. Each Young's modulus is Al: 68.3×10⁹ Pa, Ni:207×10⁹ Pa, Cu: 110×10⁹ Pa, Ag: 76×10⁹ Pa, Au: 80×10⁹ Pa, Pt: 152×10⁹Pa, Pd: 110×10⁹ Pa, Rh: 359×10⁹ Pa, Ru: 414×10⁹ Pa, Mo: 324×10⁹ Pa, andW: 345×10⁹ Pa. The Young's modulus of the first conductive powder can be60×10⁹ to 150×10⁹ Pa in another embodiment, 60×10⁹ to 100×10⁹ Pa inanother embodiment.

The first conductive powder is a metal powder having an electricalconductivity 1.00×10⁷ Siemens per meter (S/m) or more at 293 Kelvin inanother embodiment. The first conductive powder can comprise a metalselected from the group consisting of aluminum (Al: 3.64×10⁷ S/m),nickel (Ni: 1.45×10⁷ S/m), copper (Cu: 5.81×10⁷ S/m), silver (Ag:6.17×10⁷ S/m), gold (Au: 4.17×10⁷ S/m), molybdenum (Mo: 2.10×10⁷ S/m),tungsten (W: 1.82×10⁷ S/m), alloy thereof and a mixture thereof in anembodiment.

In another embodiment, the conductive powder is a metal powder having anelectrical conductivity 3.00×10⁷ S/m or more at 293 Kelvin. The firstconductive powder can comprises a metal selected from the groupconsisting of Al, Cu, Ag, Au, alloy thereof and a mixture thereof inanother embodiment. The first conductive powder can comprise Ag, Cu,Ag—Cu alloy or a mixture thereof in another embodiment. Such metals arewidely obtainable in the market.

The first conductive powder is 10 wt % or higher in an embodiment, 28 wt% or higher in another embodiment, 51 wt % or higher in anotherembodiment, 60 wt % or higher in another embodiment, 72 wt % or higherin another embodiment, and 81 wt % or higher in still anotherembodiment, based on the total weight of the conductive powder. Thefirst conductive powder is 99 wt % or lower in an embodiment, 95 wt % orlower in another embodiment based on the total weight of the conductivepowder. Within the range, conductivity of the electrode can besufficient as shown in Example below.

There is no limitation on shape of the first conductive powder. In anembodiment, the first conductive powder is flaky, spherical, or nodular,or a mixture thereof in shape in an embodiment. In another embodiment,the first conductive powder is flaky in shape. The flaky powder couldincrease contact area of the each other, consequently could rendersufficient conductivity to the formed electrode.

There is no restriction on the particle size of the conductive powder.The particle diameter (D50) can be 0.1 to 50 μm in an embodiment, 1 to35 μm in another embodiment, 1.5 to 19 μm in another embodiment.

The particle diameter is obtained by measuring the distribution of theparticle diameters by using a laser diffraction scattering method. Themedian which is 50th percentile of the particle size distribution asmeasured by volume is defined as D50 to represent the particle diameter.Microtrac model X-100 is an example of the commercially-availabledevices that can be used for this measurement.

(ii) Second Conductive Powder

The second conductive powder is made of any conductive material havingelectrical conductivity having Young's modulus of 5×10⁹ to 50×10⁹ Pa.

The second conductive powder can comprises an electrically conductivematerial selected from the group consisting of tin (Sn), bismuth (Bi),lead (Pb), indium (In), gallium (Ga), and a mixture thereof in anembodiment. Each Young's modulus is Sn: 41.4×10⁹ Pa, Bi: 31.7×10⁹ Pa,Pb: 14×10⁹ Pa, In: 10.8×10⁹ Pa, and Ga: 9.8×10⁹ Pa. The secondconductive powder comprises Sn, Bi, an alloy thereof or a mixturethereof in an embodiment.

The volume resistivity of the pressed electrode can lower by adding thesecond conductive powder as shown in Example below. The conductivepowder can comprise a metal selected from the group consisting of Sn,Bi, alloy thereof and a mixture thereof.

The second conductive powder is 1 wt % or higher in an embodiment, 3 wt% or higher in another embodiment, 5 wt % or higher in anotherembodiment, 10 wt % or higher in another embodiment, and 35 wt % orhigher in still another embodiment, based on the total weight of theconductive powder. The second conductive powder is 90 wt % or lower inan embodiment, 82 wt % or lower in another embodiment, 70 wt % or lowerin another embodiment, 51 wt % or lower in another embodiment, 42 wt %or lower in another embodiment, 27 wt % or lower in another embodiment,and 10 wt % or lower in still another embodiment, based on the totalweight of the conductive powder. Within the range, conductivity of theelectrode can be sufficient as shown in Example below.

There is no limitation on shape of the second conductive powder. In anembodiment, the second conductive powder is flaky, spherical, ornodular, or a mixture thereof in shape in an embodiment. In anotherembodiment, the second conductive powder is spherical.

The particle diameter (D50) of the second conductive powder can be 1 to50 μm in an embodiment, 2.5 to 42 μm in another embodiment, 5 to 35 μmin another embodiment. The particle diameter (D50) is obtained as wellas the first conductive powder described above.

When the first conductive powder comprises a noble metal such as Ag, Au,Pt, and Pd, the noble metal consumption can be reduced by mixing thesecond conductive powder.

In an embodiment, the first conductive powder is 8 to 50 wt % of Cupowder and the second conductive powder is 50 to 92 wt % of Sn powderbased on the weight of the conductive powder.

(b) Organic Vehicle

The conductive powder is dispersed into the organic vehicle to form aviscous composition called “paste”, having suitable viscosity forapplying on a substrate with a desired pattern.

There is no restriction on the composition of the organic vehicle. Theorganic vehicle can comprise at least an organic polymer and optionallya solvent in an embodiment.

A wide variety of inert viscous materials can be used as the organicpolymer. The organic polymer can comprise thermosetting resin,thermoplastic resin, or a mixture thereof.

The thermosetting resin can be epoxy resin, melamine resin, urea resin,unsaturated polyester resin, alkyd resin, polyurethane resin, anorganic-inorganic hybrid resin or a mixture thereof.

The thermoplastic resin can be phenol resin, polyethylene,polypropylene, polyethylene terephthalate, polyamide, polyamide-imide,acrylic resin, phenoxy resin, cellulose resin or a mixture thereof.

The organic polymer comprises a mixture of the thermosetting resin andthe thermoplastic resin, such as a mixture of epoxy resin and phenoxyresin.

The organic polymer can be 1 to 10 parts by weight in an embodiment, 1.5to 7 parts by weight in another embodiment.

In the event of the photosensitive conductive paste, the organic vehiclefurther comprises a photopolymerization initiator and aphotopolymerizable compound. The conductive paste that contains theorganic vehicle including the photo-polymerization initiator and aphoto-polymerizable compound can be cured by being exposed to light inthe photolithographic method.

The photo-polymerization initiator is a compound that generates a freeradical when it is exposed to an actinic ray. The photo-polymerizationinitiator can be, for example ethyl 4-dimethyl aminobenzoate (EDAB),diethylthioxanthone (DETX), and2-Methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one. Thephoto-polymerization initiator can be 0.1 to 3 parts by weight in anembodiment.

The photo-polymerization compound can comprise an organic monomer or anoligomer that includes ethylenic unsaturated compounds having at leastone polymerizable ethylene group. Examples of the photo-polymerizationcompound are ethocylated (6) trimethylolpropane triacrylate, anddipentaerythritol pentaacrylate. The photo-polymerization compound canbe 3 to 10 parts by weight in an embodiment.

In the event of the photosensitive conductive paste, the organic polymercan comprise acrylic polymer having a side chain of a hydroxyl group ora carboxyl group, hydroxyethyl cellulose, hydroxypropyl cellulose,hydroxyethyl hydroxypropyl cellulose or a mixture thereof. The acrylicpolymer and the cellulose can be soluble in the aqueous solution such as0.4% sodium carbonate solution in the step of developing the exposedpaste.

For the photosensitive conductive paste, US5143819, US5075192,US5032490, US7655864 can be herein incorporated by reference.

The solvent such as dibasic ester, texanol and terpineol can be used toadjust the viscosity of the conductive paste to be preferable forapplying onto the substrate. The solvent can be 5 to 35 parts by weightin an embodiment.

The organic vehicle can be, to 100 parts by weight of conductive powder,5 to 90 parts by weight in an embodiment, 7 to 61 parts by weight inanother embodiment, 9 to 42 parts by weight in another embodiment.

The organic vehicle can further comprise an organic additive such as adispersing agent, a stabilizer and a plasticizer in an embodiment.

The conductive paste can further comprise an inorganic additive such asa metal oxide or a color pigment and/or an organic additive such as adispersant and a surfactant.

The viscosity of the conductive paste can be 5 to 300 Pascal second inan embodiment, 8 to 100 Pa·s in another embodiment. The viscosity can bemeasured with a viscometer Brookfield HBT using a spindle #14 at 10 rpmat room temperature.

Example

The present invention is illustrated by, but is not limited to, thefollowing examples.

The electrode was formed with the heat-curable conductive paste.

18 parts by weight of dibasic ester (DBE-9 from INVISTA Inc.) as thesolvent and 2 parts by weight of phenoxy resin were mixed together at100° C. until the resin dissolved to form the organic vehicle.

100 parts by weight of the conductive powder was dispersed well into theorganic vehicle to form the heat-curable conductive paste. Theconductive powder contained the first conductive powder and the secondconductive powder.

The amount of the first conductive powder and the second conductivepowder based on the weight of the conductive powder was shown in Table1.

The conductive powders were as follows.

First conductive powder: flaky Ag powder with D50 of 4 μm (SF-77A, FerroCorporation) in Example 1 to 7; spherical Cu powder with D50 of 3 μm(6030, Carpenter Technology Corporation) in Example 8 and 9; flaky Cupowder with D50 of 3.2 μm (1200YP, Mitsui mining & smelting CO., Ltd.)in Example 10. Young's modules were Ag: 76×10⁹ Pa and Cu: 110×10⁹ Pa.

Second conductive powder: spherical Sn powder (AT-Sn No. 600, YamaishiMetal Co., LTd.) with D50 of 8 μm in Example 1 to 4 and Example 8 and 9;spherical Bi powder with D50 of 30 μm (BIE11PB, Kojundo chemicallaboratory); spherical Bi powder with D50 of 16 μm (Bi99.9, HikariMaterial Industory Co., Ltd.). Young's modules were Sn: 41.4×10⁹ Pa andBi: 31.7×10⁹ Pa.

The viscosity of the conductive paste was 50 Pa·s as measured with aviscometer Brookfield HBT using a spindle #14 at 10 rpm at roomtemperature.

The degree of the dispersion was measured by fineness of grind (FOG). Atypical FOG value was adjusted to 20/10 or less.

The conductive paste was screen printed through a 250 mesh screen maskonto a PET film substrate.

The electrode was obtained by heating the applied conductive paste at80° C. for 10 minutes. The pattern of the electrode was 50 mm squarewith thickness of 10 μm.

The electrode was pressed through a hydraulic calendar roll (Yuri rollCo., Ltd.) having two rolls to press at linear pressure of 61 kN/m androll speed of 1 m/min.

The pressed electrode was heated again at 150° C. for 30 minutes tofirmly cure.

Measurement

The volume resistivity of the formed electrode was measured with aresistivity meter (LORESTA-GP from Mitsubishi Chemical Co., Ltd.) beforecalendar pressing as well as after the calendar pressing.

Result

Pictures of the electrode surface before pressing and after pressingwhich were taken in Example 3 (upper) and Example 6 (lower) are shown asreferences in FIG. 3 where the Sn powder or the Bi powder deformed tomake the electrode surface flat after calendar press.

The volume resistivity of the electrode after pressing lowereddrastically in all examples using both the first conductive powder andsecond conductive powder regardless of the mixing ratio (Example 1 to10) as shown in Table 1.

In Example 1 to 3 and 5 and 6, the volume resistivity of the electrodeafter pressing was lower than 16.0×10⁻⁵ Ω·cm while an Ag electrode whichcontained only Ag powder and no second conductive powder obtained19.1×10⁻⁵ Ω·cm without being pressed. In Example 8 to 10, the volumeresistivity of the electrode lowered down to measurable level afterpressing while a non-pressed Cu electrode contained only Cu powder andno Sn powder or Bi powder got too high volume resistivity to measure.

TABLE 1 Volume Resistivity 1st conductive 2nd conductive (Ω · cm) powder(wt %)* powder (wt %)* Before After Ag Cu Sn Bi Calendar CalendarExample 1 93 0 7 0 14.9 × 10⁻⁵ 2.6 × 10⁻⁵ Example 2 60 0 40 0 18.7 ×10⁻⁵ 6.0 × 10⁻⁵ Example 3 35 0 65 0 65.0 × 10⁻⁵ 15.3 × 10⁻⁵  Example 420 0 80 0  479 × 10⁻⁵ 24.5 × 10⁻⁵  Example 5 91 0 0 9 16.3 × 10⁻⁵ 1.8 ×10⁻⁵ Example 6 58 0 0 42 13.1 × 10⁻⁵ 2.0 × 10⁻⁵ Example 7 11 0 0 89 11.5× 10⁻⁵ 7.3 × 10⁻⁵ Example 8 0 81 19 0 —** 1.1 × 10³  Example 9 0 38 62 0—** 22.0 Example 10 0 47 0 53 —** 7.9 × 10³  *Weight percent based onthe weight of the conductive powder **The volume resistivity was toohigh to measure.

What is claimed is:
 1. A method of manufacturing a non-firing typeelectrode comprising steps of: (A) applying on a substrate a conductivepaste comprising, (a) a conductive powder comprising, (i) a firstconductive powder having Young's modulus of 60×10⁹ Pa or higher, and(ii) a second conductive powder having Young's modulus of 5×10⁹ to50×10⁹ Pa; and (b) an organic vehicle; (B) heating the appliedconductive paste at 50 to 350° C. to form an electrode; and (C) pressingthe electrode at 10 to 1000 kN/m² of plane surface pressure or at 5 to300 kN/m of linear pressure.
 2. The method of claim 1, wherein theelectrode is pressed at 5 to 300 kN/m of linear pressure by a roll. 3.The method of claim 2, wherein the roll is a calendar roll and thesubstrate with the electrode is a continuous roll and pressed with thecalendar roll in a roll to roll system.
 4. The method of claim 3,wherein the substrate is a polymer film.
 5. The method of claim 1,wherein the conductive paste comprises (i) 100 parts by weight of aconductive powder and (ii) 5 to 90 parts by weight of an organicvehicle.
 6. The method of claim 1, wherein the first conductive powdercomprising a conductive material selected from the group consisting ofaluminum (Al), nickel (Ni), copper (Cu), silver (Ag), gold (Au),platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), molybdenum(Mo), tungsten (W), alloy thereof and a mixture thereof.
 7. The methodof claim 1, wherein the second conductive powder comprises a metalselected from the group consisting of tin (Sn), bismuth (Bi), lead (Pb),indium (In), gallium (Ga), alloy thereof and a mixture thereof.
 8. Themethod of claim 1, wherein the first conductive powder is 8 to 99 wt %and the second conductive powder is 1 to 92 wt % based on the weight ofthe conductive powder.
 9. The method of claim 1, wherein the electrodeis heated at 50 to 120° C. in the heating step (B) and the electrode isheated again at 100 to 350° C. after the pressing step (C).
 10. Themethod of claim 1, wherein the first conductive powder is 8 to 50 wt %of Cu powder and the second conductive powder is 50 to 92 wt % of Snpowder based on the weight of the conductive powder.
 11. An electricaldevice comprising the non-firing type electrode manufactured by themethod of claim 1.